Extreme redox variations in a superdeep diamond from a subducted slab.

The introduction of volatile-rich subducting slabs to the mantle may locally generate large redox gradients, affecting phase stability, element partitioning and volatile speciation1. Here we investigate the redox conditions of the deep mantle recorded in inclusions in a diamond from Kankan, Guinea. Enstatite (former bridgmanite), ferropericlase and a uniquely Mg-rich olivine (Mg# 99.9) inclusion indicate formation in highly variable redox conditions near the 660 km seismic discontinuity. We propose a model involving dehydration, rehydration and dehydration in the underside of a warming slab at the transition zone-lower mantle boundary. Fluid liberated by dehydration in a crumpled slab, driven by heating from the lower mantle, ascends into the cooler interior of the slab, where the H2O is sequestered in new hydrous minerals. Consequent fractionation of the remaining fluid produces extremely reducing conditions, forming Mg-end-member ringwoodite. This fractionating fluid also precipitates the host diamond. With continued heating, ringwoodite in the slab surrounding the diamond forms bridgmanite and ferropericlase, which is trapped as the diamond grows in hydrous fluids produced by dehydration of the warming slab.

Sublithospheric diamond ages and the supercontinent cycle.

Subduction related to the ancient supercontinent cycle is poorly constrained by mantle samples. Sublithospheric diamond crystallization records the release of melts from subducting oceanic lithosphere at 300-700 km depths1,2 and is especially suited to tracking the timing and effects of deep mantle processes on supercontinents. Here we show that four isotope systems (Rb-Sr, Sm-Nd, U-Pb and Re-Os) applied to Fe-sulfide and CaSiO3 inclusions within 13 sublithospheric diamonds from Juína (Brazil) and Kankan (Guinea) give broadly overlapping crystallization ages from around 450 to 650 million years ago. The intracratonic location of the diamond deposits on Gondwana and the ages, initial isotopic ratios, and trace element content of the inclusions indicate formation from a peri-Gondwanan subduction system. Preservation of these Neoproterozoic-Palaeozoic sublithospheric diamonds beneath Gondwana until its Cretaceous breakup, coupled with majorite geobarometry3,4, suggests that they accreted to and were retained in the lithospheric keel for more than 300 Myr during supercontinent migration. We propose that this process of lithosphere growth-with diamonds attached to the supercontinent keel by the diapiric uprise of depleted buoyant material and pieces of slab crust-could have enhanced supercontinent stability.

Deep continental roots and cratons.

The formation and preservation of cratons-the oldest parts of the continents, comprising over 60 per cent of the continental landmass-remains an enduring problem. Key to craton development is how and when the thick strong mantle roots that underlie these regions formed and evolved. Peridotite melting residues forming cratonic lithospheric roots mostly originated via relatively low-pressure melting and were subsequently transported to greater depth by thickening produced by lateral accretion and compression. The longest-lived cratons were assembled during Mesoarchean and Palaeoproterozoic times, creating the stable mantle roots 150 to 250 kilometres thick that are critical to preserving Earth's early continents and central to defining the cratons, although we extend the definition of cratons to include extensive regions of long-stable Mesoproterozoic crust also underpinned by thick lithospheric roots. The production of widespread thick and strong lithosphere via the process of orogenic thickening, possibly in several cycles, was fundamental to the eventual emergence of extensive continental landmasses-the cratons.

Plume-driven recratonization of deep continental lithospheric mantle.

Cratons are Earth's ancient continental land masses that remain stable for billions of years. The mantle roots of cratons are renowned as being long-lived, stable features of Earth's continents, but there is also evidence of their disruption in the recent1-6 and more distant7-9 past. Despite periods of lithospheric thinning during the Proterozoic and Phanerozoic eons, the lithosphere beneath many cratons seems to always 'heal', returning to a thickness of 150 to 200 kilometres10-12; similar lithospheric thicknesses are thought to have existed since Archaean times3,13-15. Although numerous studies have focused on the mechanism for lithospheric destruction2,5,13,16-19, the mechanisms that recratonize the lithosphere beneath cratons and thus sustain them are not well understood. Here we study kimberlite-borne mantle xenoliths and seismology across a transect of the cratonic lithosphere of Arctic Canada, which includes a region affected by the Mackenzie plume event 1.27 billion years ago20. We demonstrate the important role of plume upwelling in the destruction and recratonization of roughly 200-kilometre-thick cratonic lithospheric mantle in the northern portion of the Slave craton. Using numerical modelling, we show how new, buoyant melt residues produced by the Mackenzie plume event are captured in a region of thinned lithosphere between two thick cratonic blocks. Our results identify a process by which cratons heal and return to their original lithospheric thickness after substantial disruption of their roots. This process may be widespread in the history of cratons and may contribute to how cratonic mantle becomes a patchwork of mantle peridotites of different age and origin.

Kimberlites reveal 2.5-billion-year evolution of a deep, isolated mantle reservoir.

The widely accepted paradigm of Earth's geochemical evolution states that the successive extraction of melts from the mantle over the past 4.5 billion years formed the continental crust, and produced at least one complementary melt-depleted reservoir that is now recognized as the upper-mantle source of mid-ocean-ridge basalts1. However, geochemical modelling and the occurrence of high 3He/4He (that is, primordial) signatures in some volcanic rocks suggest that volumes of relatively undifferentiated mantle may reside in deeper, isolated regions2. Some basalts from large igneous provinces may provide temporally restricted glimpses of the most primitive parts of the mantle3,4, but key questions regarding the longevity of such sources on planetary timescales-and whether any survive today-remain unresolved. Kimberlites, small-volume volcanic rocks that are the source of most diamonds, offer rare insights into aspects of the composition of the Earth's deep mantle. The radiogenic isotope ratios of kimberlites of different ages enable us to map the evolution of this domain through time. Here we show that globally distributed kimberlites originate from a single homogeneous reservoir with an isotopic composition that is indicative of a uniform and pristine mantle source, which evolved in isolation over at least 2.5 billion years of Earth history-to our knowledge, the only such reservoir that has been identified to date. Around 200 million years ago, extensive volumes of the same source were perturbed, probably as a result of contamination by exogenic material. The distribution of affected kimberlites suggests that this event may be related to subduction along the margin of the Pangaea supercontinent. These results reveal a long-lived and globally extensive mantle reservoir that underwent subsequent disruption, possibly heralding a marked change to large-scale mantle-mixing regimes. These processes may explain why uncontaminated primordial mantle is so difficult to identify in recent mantle-derived melts.

Tungsten-182 evidence for an ancient kimberlite source.

Globally distributed kimberlites with broadly chondritic initial 143Nd-176Hf isotopic systematics may be derived from a chemically homogenous, relatively primitive mantle source that remained isolated from the convecting mantle for much of the Earth's history. To assess whether this putative reservoir may have preserved remnants of an early Earth process, we report 182W/184W and 142Nd/144Nd data for "primitive" kimberlites from 10 localities worldwide, ranging in age from 1,153 to 89 Ma. Most are characterized by homogeneous µ182W and µ142Nd values averaging -5.9 ± 3.6 ppm (2SD, n = 13) and +2.7 ± 2.9 ppm (2SD, n = 6), respectively. The remarkably uniform yet modestly negative µ182W values, coupled with chondritic to slightly suprachondritic initial 143Nd/144Nd and 176Hf/177Hf ratios over a span of nearly 1,000 Mya, provides permissive evidence that these kimberlites were derived from one or more long-lived, early formed mantle reservoirs. Possible causes for negative µ182W values among these kimberlites include the transfer of W with low µ182W from the core to the mantle source reservoir(s), creation of the source reservoir(s) as a result of early silicate fractionation, or an overabundance of late-accreted materials in the source reservoir(s). By contrast, two younger kimberlites emplaced at 72 and 52 Ma and characterized by distinctly subchondritic initial 176Hf/177Hf and 143Nd/144Nd have µ182W values consistent with the modern upper mantle. These isotopic compositions may reflect contamination of the ancient kimberlite source by recycled crustal components with µ182W ≥ 0.

Evidence for complex iron oxides in the deep mantle from FeNi(Cu) inclusions in superdeep diamond.

The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth's mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth's mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)Σ=3.95O5 We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.

Highly saline fluids from a subducting slab as the source for fluid-rich diamonds.

The infiltration of fluids into continental lithospheric mantle is a key mechanism for controlling abrupt changes in the chemical and physical properties of the lithospheric root, as well as diamond formation, yet the origin and composition of the fluids involved are still poorly constrained. Such fluids are trapped within diamonds when they form and so diamonds provide a unique means of directly characterizing the fluids that percolate through the deep continental lithospheric mantle. Here we show a clear chemical evolutionary trend, identifying saline fluids as parental to silicic and carbonatitic deep mantle melts, in diamonds from the Northwest Territories, Canada. Fluid-rock interaction along with in situ melting cause compositional transitions, as the saline fluids traverse mixed peridotite-eclogite lithosphere. Moreover, the chemistry of the parental saline fluids--especially their strontium isotopic compositions--and the timing of host diamond formation suggest that a subducting Mesozoic plate under western North America is the source of the fluids. Our results imply a strong association between subduction, mantle metasomatism and fluid-rich diamond formation, emphasizing the importance of subduction-derived fluids in affecting the composition of the deep lithospheric mantle.

Fast identification of mineral inclusions in diamond at GSECARS using synchrotron X-ray microtomography, radiography and diffraction.

Mineral inclusions in natural diamond are widely studied for the insight that they provide into the geochemistry and dynamics of the Earth's interior. A major challenge in achieving thorough yet high rates of analysis of mineral inclusions in diamond derives from the micrometre-scale of most inclusions, often requiring synchrotron radiation sources for diffraction. Centering microinclusions for diffraction with a highly focused synchrotron beam cannot be achieved optically because of the very high index of refraction of diamond. A fast, high-throughput method for identification of micromineral inclusions in diamond has been developed at the GeoSoilEnviro Center for Advanced Radiation Sources (GSECARS), Advanced Photon Source, Argonne National Laboratory, USA. Diamonds and their inclusions are imaged using synchrotron 3D computed X-ray microtomography on beamline 13-BM-D of GSECARS. The location of every inclusion is then pinpointed onto the coordinate system of the six-circle goniometer of the single-crystal diffractometer on beamline 13-BM-C. Because the bending magnet branch 13-BM is divided and delivered into 13-BM-C and 13-BM-D stations simultaneously, numerous diamonds can be examined during coordinated runs. The fast, high-throughput capability of the methodology is demonstrated by collecting 3D diffraction data on 53 diamond inclusions from Juína, Brazil, within a total of about 72 h of beam time.

Dense hydrated Mg-silicates in diamond: Implications for transport of H2O into the mantle.

Water in Earth's upper mantle is a minor and yet critically important component that dictates mantle properties such as strength and melting behavior. Minerals with stoichiometric water, such as those of the humite group, are important yet poorly characterized potential reservoirs for volatiles in the upper mantle. Here, we report observation of hydroxyl members of the humite group as inclusions in mantle-derived diamond. Hydroxylchondrodite and hydroxylclinohumite were found coexisting with olivine, magnesiochromite, Mg-bearing calcite, dolomite, quartz, mica, and a djerfisherite-group mineral in a diamond from Brazil. The olivine is highly forsteritic (Mg# 97), with non-mantle-like oxygen isotope composition (δ18O +6.2‰), and is associated with fluid inclusions and hydrous minerals-features that could be inherited from a serpentinite protolith. Our results constitute direct evidence for the presence of deserpentinized peridotitic protoliths in subcratonic mantle keels, placing important constraints on the stability of hydrous phases in the mantle and the origin of diamond-forming fluids.

Widespread PREMA in the upper mantle indicated by low-degree basaltic melts.

Studies of ocean island basalts have identified a Prevalent Mantle (PREMA) component as a fundamental feature of mantle geochemical arrays; however, its origin and distribution are highly controversial, including its potential link to plumes sourced in low-shear-wave velocity provinces (LLSVPs) above the core-mantle boundary. In this study, we interrogate the compositional systematics of ~ 3500 Cenozoic oceanic and continental sodic basalts to provide insights into the origin and distribution of PREMA. We find that low-degree basaltic melts with high Nb concentrations located away from deep-mantle plumes have PREMA-like Sr-Nd-Hf isotopic signatures, implying that PREMA is highly fusible and not exclusively associated with LLSVPs. Geochemical modelling and mantle convection simulations indicate that PREMA could have been generated soon after Earth accretion, experiencing only minimal melting or enrichment, and then scattered throughout the upper mantle, rather than being the result of mixing between depleted and enriched mantle components.

Diamond preservation in the lithospheric mantle recorded by olivine in kimberlites.

The diamond potential of kimberlites is difficult to assess due to several mantle and magmatic processes affecting diamond content. Traditionally, initial evaluations are based on the compositions of mantle-derived minerals (garnet, chromite, clinopyroxene), which allow an assessment of pressure-temperature conditions and lithologies suitable for diamond formation. Here we explore a complementary approach that considers the conditions of diamonds destruction by interaction with melts/fluids (metasomatism). We test the hypothesis that carbonate-rich metasomatism related to kimberlite melt infiltration into the deep lithosphere is detrimental to diamond preservation. Our results show that high diamond grades in kimberlites worldwide are exclusively associated with high-Mg/Fe olivine, which corresponds to mantle lithosphere minimally affected by kimberlite-related metasomatism. Diamond dissolution in strongly metasomatised lithosphere containing low-Mg/Fe olivine provides a causal link to the empirical associations between low diamond grades, abundant Ti-Zr-rich garnets and kimberlites with high Ti and low Mg contents. This finding show-cases olivine geochemistry as a viable tool in diamond exploration.

Ni isotopes provide a glimpse of Earth's pre-late-veneer mantle.

Moderately siderophile (e.g., Ni) and highly siderophile elements (HSEs) in the bulk silicate Earth (BSE) are believed to be partly or near-completely delivered by late accretion after the depletion caused by metallic core formation. However, the extent and rate of remixing of late-accreted materials that equilibrated with Earth's pre-late-veneer mantle have long been debated. Observing evidence of this siderophile element-depleted pre-late-veneer mantle would provide powerful confirmation of this model of early mantle evolution. We find that the mantle source of the ~3.8-billion-year-old (Ga) Narssaq ultramafic cumulates from Southwest Greenland exhibits a subtle 60Ni/58Ni excess of ~0.05 per mil and contains a clear HSE deficiency of ~60% relative to the BSE. The intermediate Ni isotopic composition and HSE abundances of the ~3.8-Ga Narssaq mantle mark a transitional Eoarchean snapshot as the poorly mixed 3.8-Ga mantle containing elements of pre-late-veneer mantle material transitions to modern Earth's mantle.

Comment on "Discovery of davemaoite, CaSiO3-perovskite, as a mineral from the lower mantle".

Tschauner et al. (Reports, 11 November 2021, p. 891) present evidence that diamond GRR-1507 formed in the lower mantle. Instead, the data support a much shallower origin in cold, subcratonic lithospheric mantle. X-ray diffraction data are well matched to phases common in microinclusion-bearing lithospheric diamonds. The calculated bulk inclusion composition is too imprecise to uniquely confirm CaSiO3 stoichiometry and is equally consistent with inclusions observed in other lithospheric diamonds.

Curcumin ameliorates oxaliplatin-induced chemoresistance in HCT116 colorectal cancer cells in vitro and in vivo.

The aims of this study were to determine potency of oxaliplatin in combination with curcumin in oxaliplatin-resistant cell lines in vitro and to evaluate the efficacy of a novel curcumin formulation (Meriva®) alone and in combination with oxaliplatin in colorectal tumor-bearing mice, exploring relevant pharmacodynamic markers in vivo. Oxaliplatin-resistant HCT116 p53wt and p53(-/-) cell lines were generated, and the effects of oxaliplatin in combination with curcumin on resistance- and proliferation-associated proteins investigated. Eighty nude mice were implanted with HCT116 p53wt colorectal cancer cells before randomization into the following treatment groups: control; Meriva only; oxaliplatin only; Meriva + oxaliplatin. Tumor volume was assessed, as was the expression of Ki-67, cleaved caspase-3 and Notch-1. Curcumin in combination with oxaliplatin was able to decrease proliferative capacity of oxaliplatin-resistant p53 wildtype and p53(-/-) cell lines more effectively than oxaliplatin alone. It also decreased markers associated with proliferation. After 21 days of treatment in the xenograft model, the order of efficacy was combination > Meriva > oxaliplatin > control. The decrease in tumor volume when compared to vehicle-treated animals was 53, 35 and 16%, respectively. Ki-67 and Notch-1 immunoreactivity was decreased by the combination when compared to vehicle-treated animals, with cleaved caspase-3 rising by 4.4-fold. Meriva did not adversely affect the DNA-platinating ability of oxaliplatin. Curcumin enhanced the cytotoxicity of oxaliplatin in models of oxaliplatin resistance in vitro. In vivo, Meriva greatly enhanced oxaliplatin efficacy, without affecting the mode of action of oxaliplatin. Addition of formulated curcumin to oxaliplatin-based chemotherapy regimens has the potential for clinical benefit.

Oxidation state and metasomatism of the lithospheric mantle beneath the Rae Craton, Canada: strong gradients reflect craton formation and evolution.

We present the first oxidation state measurements for the subcontinental lithospheric mantle (SCLM) beneath the Rae craton, northern Canada, one of the largest components of the Canadian shield. In combination with major and trace element compositions for garnet and clinopyroxene, we assess the relationship between oxidation state and metasomatic overprinting. The sample suite comprises peridotite xenoliths from the central part (Pelly Bay) and the craton margin (Somerset Island) providing insights into lateral and vertical variations in lithospheric character. Our suite contains spinel, garnet-spinel and garnet peridotites, with most samples originating from 100 to 140 km depth. Within this narrow depth range we observe strong chemical gradients, including variations in oxygen fugacity (ƒO2) of over 4 log units. Both Pelly Bay and Somerset Island peridotites reveal a change in metasomatic type with depth. Observed geochemical systematics and textural evidence support the notion that Rae SCLM developed through amalgamation of different local domains, establishing chemical gradients from the start. These gradients were subsequently modified by migrating melts that drove further development of different types of metasomatic overprinting and variable oxidation at a range of length scales. This oxidation already apparent at ~ 100 km depth could have locally destabilised any pre-existing diamond or graphite.

Kimberlite genesis from a common carbonate-rich primary melt modified by lithospheric mantle assimilation.

Quantifying the compositional evolution of mantle-derived melts from source to surface is fundamental for constraining the nature of primary melts and deep Earth composition. Despite abundant evidence for interaction between carbonate-rich melts, including diamondiferous kimberlites, and mantle wall rocks en route to surface, the effects of this interaction on melt compositions are poorly constrained. Here, we demonstrate a robust linear correlation between the Mg/Si ratios of kimberlites and their entrained mantle components and between Mg/Fe ratios of mantle-derived olivine cores and magmatic olivine rims in kimberlites worldwide. Combined with numerical modeling, these findings indicate that kimberlite melts with highly variable composition were broadly similar before lithosphere assimilation. This implies that kimberlites worldwide originated by partial melting of compositionally similar convective mantle sources under comparable physical conditions. We conclude that mantle assimilation markedly alters the major element composition of carbonate-rich melts and is a major process in the evolution of mantle-derived magmas.

Spatial assessment of major and trace element concentrations from Lower Athabasca Region Trout-perch (Percopsis omiscomaycus) otoliths.

The Lower Athabasca Region (LAR) is home to the largest bitumen deposit in Alberta, and has seen industrial development related to the extraction and processing of bituminous sands since the late 1960s. Along with industrial and economic growth related to oil sands development, environmental concerns have increased in recent decades, including those about potential effects on fish. We measured major and trace element concentrations in Trout-perch otoliths from the Athabasca and Clearwater Rivers in the LAR, to illustrate spatial variations and identify possible industrial impacts. Both laser ablation ICP-MS and solution-based ICP-MS methods were employed. Of the trace elements enriched in bitumen (V, Ni, Mo and Re), only Ni and Re were above the limits of detection using at least one of the methods. The only significant differences in element concentrations between upstream and downstream locations were found for Li, Cu, and Pb which were more abundant upstream of industry. For comparison and additional perspective, otoliths from the same fish species, but taken from the Batchawana River in northern Ontario, were also examined. The fish from Alberta yielded greater concentrations of Ba, Bi, Li, Mg, Na, Re, Sc, Th and Y, but the Ontario fish had more Cr, Rb and Tl, likely because of differences in geology.

Substituted beta-cyclodextrin and calix[4]arene as encapsulatory vehicles for platinum(II)-based DNA intercalators.

The encapsulation of three platinum(II)-based anticancer complexes, [(5,6-dimethyl-1,10-phenanthroline)(1 S,2 S-diaminocyclohexane)platinum(II)] (2+) ( 56MESS), [(5,6-dimethyl-1,10-phenanthroline)(1 R,2 R-diaminocyclohexane)platinum(II)] (2+) ( 56MERR), and [(5,6-dimethyl-1,10-phenanthroline)(ethylenediamine)platinum(II)] (2+) ( 56MEEN), with carboxylated-beta-cyclodextrin (c-beta-CD) and p-sulfonatocalix[4]arene (s-CX[4]) has been examined by one- and two-dimensional (1)H nuclear magnetic resonance (NMR) spectroscopy, pulsed gradient spin-echo NMR, ultraviolet spectrophotometry, glutathione degradation experiments, and growth inhibition assays. Titration of any of the three metal complexes with c-beta-CD resulted in 1:1 encapsulation complexes with the cyclodextrin located over the intercalating ligand of the metal complexes, with a binding constant of 10 (4)-10 (5) M (-1). In addition to binding over the phenanthroline ligand of 56MEEN, c-beta-CD was also found to portal bind to the ethylenediamine ligand, with fast exchange kinetics on the NMR timescale between the two binding sites. In contrast, the three metal complexes all formed 2:2 inclusion complexes with s-CX[4] where the two metal complexes stacked in a head-to-tail configuration and were capped by the s-CX[4] molecules. Interestingly, the 56MEEN-s-CX[4] complex appeared to undergo a thermodynamically controlled rearrangement to a less soluble complex over time. Encapsulation of the metal complexes in either c-beta-CD or s-CX[4] significantly decreased the metal complexes' rate of diffusion, consistent with the formation of larger particle volumes. Encapsulation of 56MESS within s-CX[4] or c-beta-CD protected the metal complex from degradation by reduced L-glutathione, with a reaction half-life greater than 9 days. In vitro growth inhibition assays using the LoVo human colorectal cancer cell line showed no significant change in the cytotoxicity of 56MESS when encapsulated by either s-CX[4] or c-beta-CD.